CN1100103C - Reaction-type neutral rosin resin - Google Patents
Reaction-type neutral rosin resin Download PDFInfo
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- CN1100103C CN1100103C CN98113987A CN98113987A CN1100103C CN 1100103 C CN1100103 C CN 1100103C CN 98113987 A CN98113987 A CN 98113987A CN 98113987 A CN98113987 A CN 98113987A CN 1100103 C CN1100103 C CN 1100103C
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- rosin
- reaction
- addition reaction
- hours
- sizing
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- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 title claims abstract description 49
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 title claims abstract description 49
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 230000007935 neutral effect Effects 0.000 title claims abstract description 20
- 238000006757 chemical reactions by type Methods 0.000 title abstract 3
- 239000011347 resin Substances 0.000 title abstract 2
- 229920005989 resin Polymers 0.000 title abstract 2
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- 238000007259 addition reaction Methods 0.000 claims description 30
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 239000000376 reactant Substances 0.000 claims description 14
- 238000005886 esterification reaction Methods 0.000 claims description 13
- 230000032050 esterification Effects 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000008064 anhydrides Chemical class 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000004513 sizing Methods 0.000 abstract description 30
- 229920001131 Pulp (paper) Polymers 0.000 abstract description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract 1
- 238000006065 biodegradation reaction Methods 0.000 abstract 1
- 125000006159 dianhydride group Chemical group 0.000 abstract 1
- 239000003292 glue Substances 0.000 description 27
- 239000000047 product Substances 0.000 description 23
- 238000001819 mass spectrum Methods 0.000 description 20
- 230000035484 reaction time Effects 0.000 description 18
- 238000009835 boiling Methods 0.000 description 11
- 238000002329 infrared spectrum Methods 0.000 description 11
- 238000005917 acylation reaction Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000009466 transformation Effects 0.000 description 10
- 239000007795 chemical reaction product Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 8
- -1 alkyl ketene dimer Chemical compound 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 229920002401 polyacrylamide Polymers 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- 235000014676 Phragmites communis Nutrition 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 3
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 3
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 159000000013 aluminium salts Chemical class 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- JESHZQPNPCJVNG-UHFFFAOYSA-L magnesium;sulfite Chemical compound [Mg+2].[O-]S([O-])=O JESHZQPNPCJVNG-UHFFFAOYSA-L 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical class CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- 150000000211 1-dodecanols Chemical class 0.000 description 1
- 102100031260 Acyl-coenzyme A thioesterase THEM4 Human genes 0.000 description 1
- 241000256844 Apis mellifera Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101000638510 Homo sapiens Acyl-coenzyme A thioesterase THEM4 Proteins 0.000 description 1
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical class N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical class CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 1
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 101150101567 pat-2 gene Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
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- Paper (AREA)
Abstract
The present invention relates to reaction-type neutral rosin resin for papermaking, which has the following general expression: in the general expression, R is C6 to C18 normal or isomeric alkyl and phenyl, Y is O or NH, X is dianhydride with more than one unsaturated link. The reaction-type neutral sizing agent can carry out sizing to paper pulp and paper pages under the conditions of neutrality and alkalescence, has the advantages of high sizing ratio, low cost, application condition fluctuation insensitivity, easy biodegradation and little pollution and does not uses aluminum salt basically.
Description
The present invention relates to add in the papermaking non-fiber material of paper pulp, particularly copy the sizing agent that paper is used.
For a long time the sizing agent used of paper industry mainly be with rosin through saponification or directly emulsification make sizing agent emulsion, as the sizing material retention agents, the rosin molecule is incorporated into fiber surface with the form of complex coordination with Tai-Ace S 150.Owing to must under acidic conditions, (PH4.5～5.5) carry out when using, therefore can produce following adverse consequences, a makes page be acidity, facile hydrolysis, embrittlement, and storage life shortens; B can not use the basic filler of super quality and competitive price; The a large amount of coating class waste paper of c can't reuse; D copies paper plain boiled water contaminate environment etching apparatus again.So International Paper's industry is copied principal direction neutrality by acidity and is copied the paper conversion.Someone is feedstock production neutral sizing agent such as cation colophony glue, rosin ester class sizing agent etc. with rosin.But the sizing agent that all belongs to non-response type still need be used retention agents such as aluminium salt sizing agent is bonded on the fiber, can not become the main product of neutral sizing agent.Afterwards people to invent out be not that the neutral sizing agent of raw material is as in U.S. Pat 2 with rosin, 627, disclosing a kind of neutral sizing agent in 477 is alkyl ketene dimer (being called for short AKD), again in U.S. Pat, 3, disclosing another kind of neutral sizing agent in 102,064 is alkenyl succinic anhydride (ASA).These two kinds of neutral sizing agents are the response type jelly, form ester bond with cellulosic hydroxyl reaction and combine in the paper-making process of page, compare with traditional acid rosin size to have applying glue efficient height, advantage such as can use under neutral, alkaline condition.But weak point is the cost costliness, and application conditions is harsh; The page frictional coefficient reduces after the applying glue, is difficult to biological degradation.
The object of the present invention is to provide that a kind of cost is low, conditional fluctuation is insensitive to using, readily biodegradable can be the neutral gum rosin of response type of basic raw material with rosin what under neutrality and the alkaline condition paper pulp and page are carried out that copying under the paper slip spare of applying glue produce that chemical bond combines with cellulosic fibre.
Purpose of the present invention can realize by following measure:
A kind ofly copy the neutral gum rosin of response type that paper uses, it is characterized in that: it has following general formula:
In the formula: R is C
6～C
18Positive structure or isomery alkyl, phenyl
Y is O or NH
X is the divalent group that has the dicarboxylic anhydride of an above unsaturated link(age).
The preparation method of the neutral gum rosin of above-mentioned response type is characterized in that:
1. the mol ratio of reactant is: rosin: alcohol or acylating agent: addition reaction=1: 1～4: 0.2～1.5; the weight ratio of rosin and catalyzer is 1: 0～2.0%; 2. the temperature of esterification or acidylate is 90～320 ℃; time is 1.5～14 hours; 3. the temperature of addition reaction is 120～220 ℃; time is 1～6 hour, 4. is reflected in the nitrogen and carries out.
Preferably the mol ratio of reactant is: rosin: alcohol or acylating agent: addition reaction=1: 1.1～1.6: 0.5～1.0, the weight ratio of rosin and catalyzer are 1: 0.5%～1.0%.The temperature of esterification or acidylate is 130～260 ℃, and the time is 6～10 hours.The temperature of addition reaction is 160～200 ℃, and the time is 2～4 hours.
Product structure general formula of the present invention is as follows:
In the formula: R is C
6～C
18Positive structure or isomery alkyl, phenyl
Y is O or NH
X is the divalent group that has the dicarboxylic anhydride of an above unsaturated link(age).
Owing to have material R, Y, the X group difference of this general formula, physico-chemical property also has very big-difference.Usually product is faint yellow extremely pale brown look thick liquid, and fusing point is at-14～6 ℃, and boiling point is at 200～300 ℃.
The preparation of product of the present invention is realized by two-step reaction.The first step is esterification or acylation reaction.1. esterification is the reaction of rosin and alcohols, and its alcohol that is suitable for is for having C
6～C
18Positive structure or the alcohols of isomery alkyl; 2. acylation reaction is the reaction of rosin and acylating agent such as amine and isocyanic acid acids, and amine that it is suitable for and isocyanic ester are for having C
6～C
18Positive structure or the amine and the isocyanates of isomery alkyl, phenyl.The consumption of rosin and alcohol or acylating agent has following proportionlity, i.e. rosin in above-mentioned reaction: alcohol or acylating agent=1: 1～4 (mol ratios), preferably 1: 1.1～1.6 (mol ratios).Above-mentioned esterification or acylation reaction can be direct and alcohol or acylation reactions of rosin; also can be under the condition that catalyzer exists, to carry out; its used catalyzer has protonic acid such as sulfuric acid, hydrochloric acid, phosphoric acid, also has lewis' acid such as zinc oxide, zinc chloride, zinc sulfate, zinc acetate to also have phosphorus trichloride, aluminum chloride and tosic acid etc.Catalyst consumption and rosin have following proportionlity, i.e. rosin: catalyzer=1: 0～2.0% (weight ratio), preferably 1: 0.5～1.0% (weight ratio).This esterification or acylation reaction are generally carried out under 90～320 ℃ of temperature, are preferably under 130～260 ℃ of temperature to carry out.React the needed time generally with 1.5～14 hours, the most handy 6～10 hours.Second step was addition reaction; be about to esterification or acidylate product that obtains and the dicarboxylic anhydride that has an above unsaturated link(age) and react, this dicarboxylic anhydride can be citraconic anhydride, tetrahydrochysene phthalic acid, MALEIC ANHYDRIDE, methylene radical maleic acid anhydride, dodecenylsuccinic acid acid anhydride etc.Dicarboxylic anhydride and rosin consumption as reactant in this addition reaction have following proportionlity, i.e. rosin: dicarboxylic anhydride=1: 0.2～1.5 (mol ratio), preferably 1: 0.5～1.0 (mol ratios).This addition reaction is generally carried out under 120～220 ℃ of temperature, preferably carries out under 160～200 ℃ of temperature.React the needed time generally at 1～6 hour, be preferably in 2～4 hours.
Product appearance of the present invention is faint yellow to pale brown look thick liquid, or paste, and (H ' NMR), mass spectrum (MS) and infrared spectra (IR) detect, and determine that this material is product innovation of the present invention to adopt proton nmr spectra.
The present invention has following advantage compared to existing technology:
1, compare with traditional gum rosin, applying glue efficient height pollutes without aluminium salt, minimizing substantially, can use under neutrality and alkaline condition.
2, compare with reactive sizing agents such as ASA, AKD, cost only is 1/6～1/2 of an above-mentioned sizing agent, and sizing efficiency is close with it.Strong to using condition adaptability, can carry out neutral sizing by the acid rosin glue system easily and transform.
Example 1
In having the reaction vessel of agitator, add 60.4 parts of rosin and 0.12 part of zinc oxide.In reaction vessel, feed nitrogen.The reacting by heating container, make rosin fusion gradually, treat to add 48.4 parts of lauryl alcohols after the whole fusions of rosin in reaction vessel, control reaction temperature was cooled to 120 ℃ at 220～260 ℃ after 6 hours, in above-mentioned product, add 20 parts of MALEIC ANHYDRIDE again, control reaction temperature is at 120～140 ℃, is flaxen sticking shape liquid through obtaining outward appearance after 3.5 hours, and the transformation efficiency of this end product is 73%, its fusing point is-6～-4 ℃, 260 ℃ of boiling points.With Finnigan MAT 3121 SS200 mass spectroscopy, operational condition is after the purification of products: acceleration voltage 3KV, and ionization voltage 70eV, sweep limit 45～500Amu, 200 ℃ of ion source temperatures, the income analysis data are: 586 (M
+, 32) and 553 (7), 541 (26), 526 (10), 470 (100), 453 (10), 354 (34), 339 (47), 302 (13), 255 (88), 187 (28), 173 (29) 121 (17).Product is analyzed through the FX90QJEOL nuclear magnetic resonance analyser again, and operational condition is a mark in the TMS, CCl
4Solution, the income analysis data are: 0.60 (3H), 0.86 (3H), 0.90～0.92 (3H), 1.02 (6H), 1.14～1.25 (20H), 1.50～1.70 (10H), 3.0～3.1 (2H), 3.95～4.10 (2H), 5.5 (1H), the structural formula through mass spectrum (MS) and proton nmr spectra (HNMR) detection conclusive evidence principal product is:
Above-mentioned product is added emulsifying agent, be prepared into 10% emulsion.The applying glue condition is: magnesium sulfite process bleached reed pulp (45 ° of SR), glue consumption 1.0% (to oven dry stock) addition of aluminum sulfate 1.0% (to oven dry stock).Polyacrylamide consumption 0.1% (to oven dry stock) is at 7.0～8.0 times applying glues of pH value, page degree of sizing 2.0mm (method of scoring).In PH8.5～9.0 time applying glue, degree of sizing 1.75mm is at PH4.5～5.5 time applying glue, degree of sizing 2.0mm.Under the same applying glue condition, use the ASA applying glue, corresponding degree of sizing is 2.0mm, 2.0mm, 1.0mm.
Example 2
Repeat the operation of example 1, wherein 60.4 parts of rosin, 77.1 parts of cetylamines, 0.6 part of catalyzer phosphorus trichloride.260～290 ℃ of acylation reaction temperature, in 8 hours reaction times, the reactant of addition reaction is a MALEIC ANHYDRIDE, its consumption is 29.4 parts.180～200 ℃ of addition reaction temperature, in 3 hours reaction times, the transformation efficiency of end product is 68%, outward appearance is yellow paste, 19～23 ℃ of fusing points, 290～294 ℃ of boiling points, mass spectrum (MS) analytical data is: 623 (M
+, 16), 608 (6), 580 (17), 597 (32), 525 (100), 257 (90), 239 (46), 213 (40), 187 (9), 113 (11), 105 (14).Proton nmr spectra (analytical data: 0.90 (3H) of H ' NMR), 0.86 (3H), 0.90～0.93 (3H), 1.04 (6H) 1.12～1.20 (10H), 1.22～1.25 (2H), 3.20～3.30 (2H), 5.5 (1H).The structural formula of confirming principal product after testing is: CH
3CONHC
16H
33 
Example 3 repeats the operation of example 1, wherein 60.4 parts of rosin, 59.4 parts of stearyl alcohol, 0.6 part on catalyst oxidation zinc.240～270 ℃ of esterification reaction temperatures, 8 hours reaction times.The reactant of addition reaction is a MALEIC ANHYDRIDE, and its consumption is 10.0 parts.160～180 ℃ of addition reaction temperature, 2.5 hours reaction times.The transformation efficiency of end product is 70%, and outward appearance is a light yellow viscous liquid, 4～6 ℃ of fusing points, and 280～284 ℃ of boiling points, mass spectrum (MS) analytical data is: 652 (M
+, 24), 609 (9), 580 (8), 526 (86), 509 (9), 410 (43), 395 (40), 339 (51), 302 (16), 255 (83), 239 (92), 213 (17), 187 (30), 173 (23).Proton nmr spectra (analytical data: 0.60 (3H) of H ' NMR), 0.86 (3H), 1.02 (6H), 1.14～1.20 (12H), 1.22～1.25 (32H), 3.01～3.10 (2H), 3.95～4.10 (2H), 5.5 (1H), confirm that after testing the structural formula of principal product is:
Repeat the operation of example 1, wherein rosin is 60.4 parts, 86.4 parts of 18 alkyl chloride, 90～120 ℃ of acylation reaction temperature, 1.5 hours reaction times.The reactant of addition reaction is a MALEIC ANHYDRIDE, and its consumption is 13.7 parts.200～220 ℃ of addition reaction temperature; 3 hours reaction times.Transformation efficiency through product is 74%, its outward appearance, fusing point, boiling point, and the structural formula of mass spectrum (MS) analytical data, proton nmr spectra (HNMR) analytical data and major product is identical with example 3.
Example 5
Repeat the operation of example 1, wherein rosin is 60.4 parts, 163.2 parts of n-hexyl alcohols, catalyzer phosphatase 11 .2 part.130～160 ℃ of esterification reaction temperatures, in 8 hours reaction times, the reactant of addition reaction is the methylene radical maleic acid anhydride, its consumption is 5.0 parts.140～160 ℃ of addition reaction temperature, 1.0 hours reaction times.The transformation efficiency of end product is 72%, and its outward appearance is a weak yellow liquid, fusing point-12 ℃, 168～170 ℃ of boiling points.Mass spectrum (MS) analytical data: 498 (M
+, 46) and 483 (6), 426 (7), 386 (19), 257 (90), 242 (63), 239 (18), 147 (16), 121 (24), 105 (17).With Perkin-Elmer FTIR-1700 infrared spectra (KBr compressing tablet) analytical data be: ν (cm
-1): 1690 (COOH) disappear 1725
Honeybee occurs, 1862,1781 (
) occur, 2855,2926 alkane occur.The structural formula of confirming principal product after testing is:
Example 6
Repeat the operation of example 1, wherein rosin is 60.4 parts, 95.2 parts of phenylethyl alcohols, 0.12 part of catalyzer tosic acid.190～210 ℃ of esterification reaction temperatures, 12 hours reaction times.The reactant of addition reaction be along methyl in the enedioic acid acid anhydride, 11.2 parts of its consumptions.180～200 ℃ of addition reaction temperature, 3 hours reaction times.The transformation efficiency 69% of end product, its outward appearance are the sticking shape liquid of tawny, 0～2 ℃ of fusing point, 212～214 ℃ of boiling points, mass spectrum (MS) analytical data, 528 (M
+, 43), 400 (31), 372 (20), 328 (19), 302 (21), 257 (100), 241 (60), 149 (80), 121 (86), 105 (100).Confirm that after testing the structural formula of producing thing is:
Example 7
Repeat the operation of example 1, wherein rosin is 60.4 parts, 104 parts of secondary octanols, 0.3 part of catalyzer zinc chloride.150～180 ℃ of esterification reaction temperatures, 14 hours reaction times.The reactant of addition reaction is the methylene radical maleic acid anhydride, and its consumption is 22.4 parts.160～180 ℃ of addition reaction temperature, 4 hours reaction times.The transformation efficiency of end product is 69%, and outward appearance is a weak yellow liquid, fusing point-8～-10 ℃, 186～190 ℃ of boiling points.Mass spectrum (MS) analytical data is: 528 (M
+, 43), 400 (31), 372 (20), 328 (19), 302 (21), 257 (100), 241 (60), 149 (80), 121 (86), 105 (100).Infrared spectra (IR) analytical data: ν (cm
-1): 1690 (COOH) peak disappears, 1725 (
) occur, 1860,
Above-mentioned product is used for sulphite bleached reed pulp (45 ° of SR) applying glue condition is: page quantification 80 gram/m
2, glue consumption 0.5% (to oven dry stock), applying glue pH value 7.0～8.0, the sub-starch consumption 1.0% in Yanggao County (to oven dry stock).Polyacrylamide consumption 0.05% (to oven dry stock), page degree of sizing 1.0mm, if applying glue pH value 5.0～6.0, page degree of sizing 1.0mm.
Example 8
Repeat the operation of example 1, wherein rosin is 60.4 parts, 59.2 parts of stearylamines, 0.6 part of catalyzer phosphorus trichloride.290～320 ℃ of acylation reaction temperature, 8 hours reaction times.The reactant of addition reaction is the dodecenylsuccinic acid acid anhydride, and its consumption is 42.6 parts.140～160 ℃ of addition reaction temperature, 6 hours reaction times.The transformation efficiency of end product is 67%, and its outward appearance is yellow hard body of paste, 40～42 ℃ of fusing points, 302～306 ℃ of boiling points.Proton nmr spectra (HNMR) analytical data: 0.60 (3H), 0.86 (3H), 0.90～0.92 (3H), 1.04 (6H), 1.12～1.18 (10H), 1.20～1.25 (40H), 3.0～3.15 (2H), 3.20～3.30 (2H), 5.5 (1H), infrared spectra (IR) analytical data, ν (cm
-1): 3460,3390,1700
1865,1780,1210 (
) 2920,2836,725, (CH2-); 1370,1380
1685,1075 (ring skeletons), confirm that after testing the structural formula of principal product is:
R wherein
1With R
2The carbon number sum is 12
Above-mentioned product is added emulsifying agent be prepared into 10% emulsion.The applying glue condition is: magnesium sulfite process bleached reed pulp 80%, poplar CTMP bleached pulp 20%, (52 ° of SR of mixed pulp), glue consumption 0.5% (to oven dry stock), cationic starch consumption 1.0%, polyacrylamide consumption 0.1% (all to oven dry stock).Applying glue pH value 7.5～8.5 under page degree of sizing 1.25mm (method of scoring) similarity condition, is used the ASA applying glue, and degree of sizing is 1.0mm.
Example 9
Repeat the operation of example 1, wherein rosin is 60.4 parts, and amine is 20.5 parts just, 0.48 part of catalyzer aluminum chloride.120～140 ℃ of acylation reaction temperature, 4 hours reaction times.The reactant of addition reaction is a citraconic anhydride, and its consumption is 11.3 parts.140～160 ℃ of addition reaction temperature, 4 hours reaction times.The transformation efficiency of end product is 71%, and its outward appearance is a yellow liquid, fusing point-16 ℃, 140～144 ℃ of boiling points.Mass spectrum (MS) analytical data: 497 (M
+, 26), 470 (9), 426 (17), 397 (14), 385 (90), 342 (26), 302 (7), 257 (49), 239 (21), 213 (32), 105 (20).Infrared spectra (IR) analytical data: ν (cm
-1): 1690 (COOH) disappear, 3420 (
) occur, 1860,1760 (
) occur.The structural formula of confirming this principal product after testing is:
Example 10
Repeat the operation of example 1, wherein rosin is 60.4 parts, 96 parts of phenylcarbimides.120～140 ℃ of acylation reaction temperature, in 3 hours reaction times, the reactant of addition reaction is the tetrahydrochysene phthalate anhydride, its consumption is 30 parts.160～180 ℃ of addition reaction temperature, 2.5 hours reaction times.The transformation efficiency of end product is 74%, and its outward appearance is a tawny liquid, fusing point-4～-2 ℃, 140～142 ℃ of boiling points.Mass spectrum (MS) analytical data: 530 (M, 17), 459 (19), 437 (31), 409 (28), 257 (70), 214 (14), 193 (18), 149 (84), 121 (46), 104 (71).Infrared spectra (IR) analytical data: ν (cm
-1): 3342,1700
1248,1780,1865 (
); 1600,1500 (ph-NH-CO).The structural formula of confirming this principal product after testing is:
Above-mentioned product is used for the applying glue of soda processes Straw Pulp, and the applying glue condition is: page quantification 80 gram/m
2, glue consumption 0.5% (to oven dry stock) applying glue pH value 7.0～7.5, amphiprotic polyacrylamide consumption 0.2% (to oven dry stock), page degree of sizing 1.25mm.Same applying glue condition adopts the ASA applying glue, page degree of sizing 1.25mm.
Annotate: the charging capacity of embodiment is parts by weight.
Claims (5)
1, a kind ofly copy the neutral gum rosin of response type that paper uses, it is characterized in that: it has following general formula:
R is C in the formula
6～C
18Positive structure or isomery alkyl, phenyl
Y is O or NH
X is the divalent group that has the dicarboxylic anhydride of an above unsaturated link(age).
2, the preparation method of the neutral gum rosin of the described response type of claim 1 is characterized in that:
1. the mol ratio of reactant is a rosin: alcohol or acylating agent: addition reaction=1: 1～4: 0.2～1.5; the weight ratio of rosin and catalyzer is 1: 0～2.0%; 2. the temperature of esterification or acidylate is 90～320 ℃; time is 1.5～14 hours; 3. the temperature of addition reaction is 120～220 ℃; time is 1～6 hour, 4. is reflected in the nitrogen and carries out, and wherein addition reaction is the dicarboxylic anhydride that has an above unsaturated link(age).
3, the preparation method of the neutral gum rosin of response type according to claim 2; it is characterized in that: the mol ratio of reactant is a rosin: alcohol or acylating agent: addition reaction=1: 1.1～1.6: 0.5～1.0, the weight ratio of rosin and catalyzer are 1: 0.5%～1.0%.
4, the preparation method of the neutral gum rosin of response type according to claim 3, it is characterized in that: the temperature of esterification or acidylate is 130～260 ℃, the time is 6～10 hours.
5, the preparation method of the neutral gum rosin of response type according to claim 4, it is characterized in that: the temperature of addition reaction is 160～200 ℃, the time is 2～4 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98113987A CN1100103C (en) | 1998-05-12 | 1998-05-12 | Reaction-type neutral rosin resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98113987A CN1100103C (en) | 1998-05-12 | 1998-05-12 | Reaction-type neutral rosin resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1238364A CN1238364A (en) | 1999-12-15 |
| CN1100103C true CN1100103C (en) | 2003-01-29 |
Family
ID=5223673
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98113987A Expired - Fee Related CN1100103C (en) | 1998-05-12 | 1998-05-12 | Reaction-type neutral rosin resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1100103C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017040021A (en) * | 2014-08-21 | 2017-02-23 | 荒川化学工業株式会社 | Rosin-based emulsion sizing agent and paper |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042727A (en) * | 1988-11-14 | 1990-06-06 | 金华市工业科学研究所 | A kind of modifying process for rosin |
-
1998
- 1998-05-12 CN CN98113987A patent/CN1100103C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042727A (en) * | 1988-11-14 | 1990-06-06 | 金华市工业科学研究所 | A kind of modifying process for rosin |
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| Publication number | Publication date |
|---|---|
| CN1238364A (en) | 1999-12-15 |
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